Alkyl glyceryl ether sulfonate mixtures and processes for preparing the same



Maw]! 1962 D. D. WHYTE ETAL 3,@%,? ALKYL GLYCERYL ETHER SULFONATEMIXTURES AND PROCESSES FOR PREPARING THE SAME Filed May 14. 1957 ak'mkINVENTORfi BY ad 3m, 89%, 415g 11 WJSM ATTORNEY5 This application is acontinuation-in-part of application Serial Number 437,246, filed June16, 1954, now abandoncd.

The present invention relates to detergent compositions.

More particularly, this invention relates to sulfonic acid salts ofhigher molecular alkyl ethers of glycerol and to a process for producingthe same.

It is known that sulfonic acid saltsof alkyl monoglyceryl ethers may beprepared by reacting epichlorohydrin with higher molecular alcohols inthe presence of a catalyst, such as stannic chloride, to form the alkylchloromonoglyceryl ethers and then subsequently converting thechloromonoglyceryl others to the sulfonic acid salts throughStrechkerization, i.e., reaction with sodium sulfite. Such a process isdescribed in US. Letters Patent 2,094,489 to Richard Hueter, grantedSeptember 28, 1937.

The sulfonic acid salts of the alkyl monoglyceryl ether produced inaccordance with the process of the above patent were found to havegooddetersive properties when the alkyl radicals were derived fromalcohols obtained from middle cut coconut fatty alcohols, ,i.e., thefatty alcohol fraction, derived from coconut oil, which predominates inalcohols having a chain length of 12 carbon atoms and which aresubstantially free of alcohols having a chain'length of 16 and 18 carbonatoms. The sulfonic acid salts of alkyl monoglyceryl ethers containingsuch high molecular weight alkyl radicals are characterizedby relativelypoor detersive performance. This is due primarily to the decreasedsolubility of the higher alkyl monoglyceryl ether sulfonates.

In the previously known methods for preparing the alkyl monoglycerylether sulfonates from a monohydroxy alcohol and an epihalohydrin, thereaction between the alcohol and epihalohydrin to form the haloglycerylether was normally conducted in the presence of an excess of alcohol.This required the removal of the unreacted alcohol from the haloglycerylether before the Streckerization reaction could be satisfactorilycarried out and therefore involved an additional distillation operation.

It is an object of this invention to produce alkyl glyceryl ethersulfonates which are characterized by good detersive properties althoughsuch products contain appreciable amounts of high molecular weight alkylgroups.

It is a further object of this invention to provide a process forproducing alkyl glyceryl ether sulfonates whereby etherification of thealcohols to form haloglyceryl ethers prior to Streckerization can becarried to substantial completion with no further purification of thehaloglyceryl ethers being necessary.

A still further object of this invention is to provide a method forpreparing detergent compositions containing alkyl glyceryl ethersulfonates which are characterized by improved solubility.

Other objects of the invention will be apparent from the followingdescription and the accompanying drawings in which:

FIGURE 1 is a graphical representation showing the composition ofproducts which are obtained in accordance with the process of theinvention in terms of the respective proportions of reactants, i.e.',epichlorohydrin and high molecular weight alcohol present; and

FIGURE 2 is a schematic diagram representing apparatus suitable for usein practicing this invention.

It has now been found that the foregoing and other objects can beaccomplished by reacting high molecular weight fatty alcohols with anamount of epichlorohydrin which is in excess of that required to reactwith the alcohol to produce the chloromonoglyceryl ether and thensulfonating the resulting chlorogyceryl ethers by means of theStreckerization reaction.

As a matter of convenience in this application whereever the termStreckerization and sulfonation' appear hereinafter, they will beconsidered to be synonymous.

The use of an excess of epichlorohydrin results in the production ofchloroglyceryl ethers in which the glyceryl radical is replaced in partwith polyglyceryl radicals, e.g. with two or three condensed glycerylradicals. The formation of such polyglyceryl ethers may be said toprogress stepwise in accordance with the following equations:

H H H H H H ROH H--7-Al-3-Cl -v RO-( J- i!Cl o it A it H H H H H H H H HRO- il--Cl H(|)-- 4 3-01 30- -J3-( JCl ii A it 0 1i i A a i l n HHC-Z-(E-Gl a l i ii dlehlorndiglycaryl ether H H H H H 'H Ito-$454541 He1 H- H ELLA-C1 5 trichlorotrlglyceryl ether H H H .Roh-h-h-Qi i 5 i i li H H HJJ-(h-h-Cl h 6 it The higher polymers, such as thetetrachloro-tetraglyceryl ethers, may also be formed, the amountdepending upon the amount of excess epichlorohydrin which is used. Inany event, the reaction product will comprise a mixture of the monomerwith various proportions of the polymers.

The mixture of chloroglyceryl ethers which is formed Patented Mar. 6,lfififi in the process of this invention can be represented by thefollowing general formula:

wherein R is an alkyl containing from about 8 to 22 carbon atoms and nis an integer from 1 to 4, said mixture comprising at least of suchethers wherein n is 2. For convenience the chloroglyceryl ethers where nis 1, 2, 3 or 4 will hereinafter be referred to respectively, as themonomer, dimer, trimer and tetramer.

The aforesaid mixture of chloroglyceryl ethers will also undoubtedlycontain positional isomers of the various ethers in minor quantity, andit is to be understood that herein and in the appended claims anyreference to the glyceryl ethers, whether in sulfonated or unsulfonatedform, is to be construed as including within its scope the positionalisomers of the said glyceryl ethers. For

example, the epoxy oxygen of the chlorohydrin may break so that theether linkage between the alcohol and glyceryl radical may attach toeither the terminal or middle carbon of the glyceryl radical. Also, theattachment of the second glyceryl radical to the first may be through anether linkage to the terminal or middle carbon atom. By way ofillustration, four of the isomeric diglyceryl ethers may be illustratedby the following structural formulations:

In preparing the alkyl chloroglyceryl ethers in accordance with theprocess of this invention at least 1.05 mols of epichlorohydrin is usedfor every one mol of alcohol which is to be reacted, i.e., at least 5%excess epichlorohydrin over the molar equivalent of alcohol is used.Reference to FIGURE 1 will serve to indicate that with about 5% molarexcess epichlorohydrin about 10% of the dimer is formed and about 7.5%(.075 mol) alcohol remains unreacted. It has been found that this amountof dimer, after subsequent sulfonation, is sufiicient to impart to theproducts of this invention the advantages associated with the presenceof the dimer. In addition, it has been found that the amount ofunreacted alcohol after subsequent sulfonation does not significantlymodify the advantageous properties of the alkyl glyceryl ethersulfonates. Hence, no additional distillation step to remove theunreacted alcohol is necessary before the sulfonation reaction iscarried out.

It can be seen from FIGURE 1 that the amount of unreacted alcoholincreases rapidly with decreasing amounts of epichlorohydrin below the5% molar excess value set forth above. Consequently, with such lesseramounts of epichlorohydrin, the unreacted alcohol must be removed fromthe ehloroglyceryl ether product before equivalent of alcohol used,increasing amounts of dimer and trimer are formed. The amounts of thesecomponcnts in the products of this invention may be readily adjusted byregulating the excess of epichlorohydrin used to obtain alkyl glycerylether sulfonates having desired properties. Then too, if desired, themixed alkyl chloroglyceryl ethers can be subjected to a distillationprocedure whereby fractions consisting essentially of hte monomer, dimerand trimer components of the aforesaid mixture can be separated. Theseseparated fractions can then subsequently be sulfonated as hereinafterdescribed.

The products of this invention which result from the Streckerization ofthe aforementiioned mixture of alkyl chloroglyceryl ethers consistessentially of a mixture of sulfonated aliphatic glyceryl ethercompounds of the general formula:

where R is an alkyl radical containing from about 8 to 22 carbon atoms,n is an integer from 1 to 4, and X is selected from the group consistingof chlorine, hydroxyl and water-soluble sulfonic acid salt radicals, atleast one X in the product being a sulfonic acid salt radical, thecation of the said sulfonic acid salts being selected from the groupconsisting of sodium, potassium, ammonium, calcium, magnesium, andalkylol-substituted ammonium in which alkylol contains a whole number ofcarbon atoms from 2 to 3, said mixture containing at least about 10% ofsuch ethers where n is 2.

Although the Streckerization reaction can be readily carried oututilizing either sodium or potassium sulfite, sulfonation with othersulfites can be accomplished only with difiiculty. Consequently, if itis desired to have salts other than the sodium or potassium salts of thealkyl glyceryl ether sulfonates, such as the calcium, magn'esium,ammonium or alkylol-substituted ammonium salts, the sodium salt, forexample, can be passed over an ion exchange resin to replace the sodiumion with a hydrogen ion and the resulting acid can then be neutralizedwith calcium or magnesium hydroxide, ammonia or alkylol-substitutcdammonia e.g., the mono-, dior triethanol or propanol amines.

In carrying out the sulfonation reaction with sodium or potassiumsulfite as the sulfonating agent, not all of the reactive groups of thechloroglyceryl ethers are converted to sulfonate radicals. For example,although upon sulfonating the dimer, the dimer disulfonate is primarilyformed, some of the chlorine radicals of the chloroglyceryl ether remainunreacted and other chlorine radicals are hydrolyzed to hydroxylradicals. As a consequence, the sulfonated dimer product comprises, forexample, a mixture of diglyceryl monohydroxy disulfonate, diglyceryldihydroxy monosulfonate, diglyceryl monochloro monohydroxy monosulfonateand a minor amount of diglyceryl trihydroxy ethers. The analysis oftypical dimer sulfonates indicates that about 50% of the dimers aremonohydroxy disulfonates, about 35% are dihydroxy monosulfonates andabout 15% are monochloro monohydroxy monosulfonates.

The presence of the dimer and trimcr sulfonatcs in the products of ourinvention offer several advantages. For example, the diand tri-glycerylether sulfonates of the high molecular weight alcohols, i.e.,thosecontaining 16-18 carbon atoms in the alkyl chain, are characterized by asolubility in cool water, i.e., water at normal dishpantemperature-about 105 E, which is comparable to the solubility of thelower molecular weight (l2-14 carbon alkyl chain) alkyl monoglyccrylether sodium sulfonates under the conditions. Moreover, the polyglycerylclerivatives of such high molecular weight alcohols are characterized bygood detersive properties either alone or when combined in substantialproportions with the sulfonic acid salts of the monoglyceryl ethers ofthe relatively lower molecular weight middle cut coconut fatty alcohols.The improved solubility of the polymeric forms of the high molecularweight alkyl glyceryl ether sulfonates as compared with the monomericform of these sulfonates offers a decided economic advantage. Forexample, hydrogenated tallow can now readily be used as the source ofthe alkyl groups of the alkyl glyceryl ether sulfonates whereas,heretofore, the alkyl groups had necessarily to be obtained from therelatively more expensive coconut oil if a product having good detersiveperformance at low temperature conditions was desired.

The present invention also makes available many other alcohols asconvenient source materials for the alkyl groups of the alkyl glycerylether sulfonate products. Thus, the fatty alcohols derived fromunhydrogenated tallow can be utilized. These will, of course, result inthe inclusion of alkenyl glyceryl ether sulfonates in the products ofthe invention. Consequently, wherever herein the term alkyl appears itis to be understood to include within its scope the alkenyls as well asthe true alkyls.

Palm oil, hydrogenated marine oil, the latter containingsome fatty acidshaving 20 and 22 carbon atoms in the alkyl chain, and oxo alcohols, madeby reacting carbon monoxide and hydrogen with olefins, also representavailable fatty alcohol sources which can be used in this invention. Y

It is to be understood that because of solubility considerations, withthe higher molecular weight alkyl glyceryl ether sulfonate products ofthis invention i.e., those glyceryl ether sulfonates containing alkylchains having from about 16 to 22 carbon atoms, it is advantageous tohave a higher proportion of dimer, trimer and tetramer present than ifthe said products contained lower molecular weight alkyl groups, i.e.,those alkyl groups containing from about 8 to 14 carbon atoms.

Advantages are also experienced from a conversion of portions of lowermolecular weight alcohols, i.e., those having l2-l4 carbon atoms in thealkyl chain, to the alkyl polyglyceryl, and especially the alkyldiglyceryl, ether sulfonates. These low molecular weight sulfonatedpolyglyceryl ethers have been found to be as efiective in theirdetersive properties as the sulfonated monoglyceryl ethers. For thisreason there is no particular advantage in the preparation and isolationof only the monoglyceryl form of the said ether sulfonates.Consequently, the mono etherification of such lower molecular weightalcohols can be carried out to substantial completion by using an excessof epichlorohydrin, which excess also promotes the formation of thedimer and trimer ethers, and no further purification of the resultingproduct ethers will be required.

It has been further found that thedimer ether sulfonate in the productsof the invention acts in the capacity of a solubilizing agent andpromotes solution of the monomer ether sulfonate present in the product.

When the alkyl glyceryl ether sulfonates of the invention are preparedutilizing the middle cut coconut alcoh'ols it is preferred that theamount of excess epichlorohydrin be adjusted so as to produce achloroglyceryl ether product which, upon sulfonation, will becharacterized by a dimer content of about to about 30%. Adjustment ofthe excess epichlorohydrin to produce a product having a dimer contentwithin the aforemen- C AIcol10I."Denotes the alcohol derived fromfreetionallydistilling the alcohols made by the reduction of coconutoil,the separated alcohol comprising about 97% alcohol containing 12 carbonatoms in the alkyl chain and having a molecular weight of about 186.

Middle C u! CN A/co/10I.-Denotes the alcohol derived from fractionallydistilling the alcohols made by the reduction of coconut oil, theseparated fraction having the following approximate composition:

2% m 66% C12 23% c 9% c The subscript denotes the number of carbon atomsin the alkyl chain.

Example 1.40O parts of C alcohol were reacted with 219 parts ofepichlorohydrin for about one half hour at C. in the presence of 9.2parts of stannic chloride as a catalyst. The amount of epichlorohydrinwas 10% in excess of the molar equivalent of alcohol.

The product ethers were water washed and a yield of 7 623.2 partswasrecovered. The fractions separated during the subsequent distillationof the recovered ethers at 5 mm. of mercury absolute pressure are setforth below.

Alcohol cut 29.3parts- 4.7%. Monomer ether 435.8 parts-70.0%. Highboilingcut (predominantly dimer ether) 71.3 parts-41.4%. Polymers andlosses 86.8 parts-13.9%.

A second alkyl chloroglyceryl ether preparation was made in accordancewith the above conditions by reacting 400 parts of C alcohol with 179parts of epichlorohy drin in the presence of 5.8 parts of stannicchloride catalyst. The epichlorohydrin was 87.5% of the molar equivalentof the alcohol. The product ethers were water washed and a yield of555.4 parts was recovered. Fractional distillation of the recoveredethers at 5 mm. of mercury, absolute pressure gave the followingresults.

Alcohol cut 94.7 parts-17.1%. Monomer ether 381.3 parts-68.6%. Residue63.1 parts-11.4%. Losses 16.3 parts- 2.9%.

A comparison of the fractions obtained from the distillation of thechloroglyceryl ether where an excess of epichlorohydrin was used withthe fractions-obtained from the distillation where no excess ofepichlorohydrin was used indicates that the product constituents areconsiderably different. Where excess epichlorohydrin was used thepolymers, including the high-boiling out which is predominately dimerether. and losses comprise 25.3 of the ethers subjected to fractionaldistillation as compared to a total of 14.3% of residue (polymers) andlosses where no excess epichlorohydrin was employed. The formation of anincreased amount of chloroglyceryl ether polymers where an excess ofepichlorohydrin is used is clearly indicated.

The data also indicate a marked decrease in the amount of the alcoholfraction when an excess of epichlorohydrin was used. This evidences amore complete utilization of 7 the alcohol reactant with the attendantadvantages hereinbefore pointed out.

Example 2.250 parts of dichlorodiglyceryl ether of dodecyl alcohol, 267parts of potassium sulfite of 96% purity and 346 parts of water wereplaced in an autoclave, were allowed to react for one hour at 375 F.,and were subsequently cooled. it was determined that 97.7% of thedichlorodiglyceryl ether was converted to a potassium salt of thesulfonate derivative. The product was highly soluble and its solutionswere mild in their action toward fabrics and the skin and possessed gooddetersive characteristics.

Example 3.-l0.35 parts of a mixture of alkyl chloroglyceryl ethers, 7.25parts of sodium sulfite having a 95% purity. and 28.4 parts of waterwere reacted for one half hour at 375 F. in an autoclave. The mixture ofchloroglyceryl others was obtained from reacting middle cut coconutalcohol with an amount of epichlorohydrin 100% in excess of the molarequivalent of the alcohol and comprised approximately 30% monomer, 44%dimer, and 26% trimer ethers. The reaction products were subsequentlycooled and it was determined that 94.5% of the ethers were converted toa sodium salt of the sulfonate derivative. The product was highlysoluble and its solutions were mild in their action toward fabrics andthe skin and possessed good detersive characteristics.

It is to be understood that in the foregoing example the miXture ofchloroglyceryl ethers obtained from reacting the alcohols resulting fromthe reduction of hydrogenated or unhydrogenated tallow, for example,with an amount of epichlorohydrin at least in excess of the molarequivalent of the alcohol, can be substituted for the coconut alkylchloroglyceryl ethers of the example with comparable results.

Example 4.13.5 parts of the mixture of alkyl chloro' glyceryl ethers,9.25 parts of sodium sulfite of 95% purity, 05 part of sodium hydroxideand 22.5 parts of water were reacted in an autoclave at 400 F. for onehalf hour. The mixture of chloroglyceryl ethers was obtained fromreacting middle cut coconut alcohol with an amount of epichlorohydrin40% in excess of the molar equivalent of the alcohol and comprisedapproximately 65% monomer, 32% dimer and 3% trimer ethers. The resultantproduct was cooled and it was determined that 93.4% of thechloroglyceryl ethers were converted to a sodium salt of the sulfonatederivative. The product was highly soluble and its solutions were mildin their action toward fabrics and the skin and possessed good detersivecharacteristics.

Example 5 .-A detergent formulation comprising 7.9% sodium alkylglyceryl ether sulfonate, 9.6% sodium tallow alkyl sulfate, 6.0%silicate solids, 50% sodium tripolyphosphate and 8% water, the remainderof the composition comprising essentially sodium sulfate, was preparedand found to be eminently suitable for general household detergent use.

The alkyl glyceryl ether sulfonate constituent of this detergentformulation was prepared in accordance with the process of theinvention. A 15% excess of epichlorohydrin was utilized to prepare amixture of alkyl chloroglyceryl ethers from middle cut coconut alcohols,and this mixture was then sulfonated to produce the alkyl glyceryl ethersulfonate constituent.

Although it is not intended that this application shall be limitedthereto, it has been found that a continuous sulfonation procedure hasmarked advantages if certain procedures are followed. It is also to beunderstood that any of the conditions set forth hereinafter indescribing a continuous sulfonation procedure are also applicable tobatch type sulfonations and that other alkali metal sulfites may bereadily substituted for sodium sulfite as the sulfonating agent.procedure will be better understood in reference to the diagramaticsketch of FIGURE 2 which is merely illustrative of apparatus suitablefor use in the process and is The preferred continuous sulfonation notto be construed as establishing limitations on applicable apparatus.

Alkyl chloroglyceryl ethers prepared in accordance with the process ofthis invention are held in storage tank 1 and a sodium sulfite solutionis held in dissolving and storage tank 6. The concentration of thesodium sulfite solution is not critical but should be such that theundried sulfonation product will contain at least 50% water. Although itis preferred to maintain the sodium sulfite .concentration in the rangewhich will result in the formation of an undried sulfonate productcontaining about 50-60% water, the sulfonation reaction will proceedsatisfactorily with a solution of sodium sulfite which will result inthe formation of an undried sulfonate product containing as much aswater. The limit on the water content of the sulfite solution isdetermined by the limit of solubility of sodium sulfite in water and byeconomic factors, such as, the decrease in the formation of activeproduct, i.e. sulfonated glyceryl ethers, because of the hydrolysis ofthe chloroglyceryl ethers which is promoted by the presence of largeamounts of water and by the economics of the subsequent dryingoperation. It has been found, for example, that with the addition of analkali metal hydroxide to control the pH during the sulfonation reactionas indicated hereinafter, sodium sulfite solutions having aconcentration as high as 17% can be utilized.

It has also been found that when potassium sulfite is utilized as thesulfonating agent, the concentration of the potassium sulfite solutionmay be such as will result in the formation of an undried sulfonateproduct containing as little as 40% water-the actual lower limit onwater content of the said undried 'sulfonate product being determinedonly by the ease with which the said product can be pumped.

The alkyl chloroglyceryl ether is pumped by metering pump 2 through thepr'eheaters 3, equipped with steam inlet 4 and steam condensate outlet5, and is heated therein to about 360 F.

The sodium sulfite solution is pumped by metering pump 7 throughpreheater 8, equipped with steam inlet 9 and steam condensate outlet 10,and is heated therein to a temperature of about 360 F. It is usual inthe practice of this process to heat both the alkyl chloroglyceryl etherand the sulfite solution to temperatures in the range from about 350 F.to 375 F. to maintain the desired temperature in the reactor.

The alkyl chloroglyceryl other and sodium sulfite solution passes frompreheaters 3 and 8 respectively into mixer 11 to which metering pump 12supplies an alkali metal hydroxide solution of such strength and in suchamounts as will maintain the pH of the mixture at a value in the rangefrom about 8 to 10. Although sulfonation will proceed at any pH in therange from about 7 to 11, it is preferred, in order to obtain maximumcompleteness of the reaction, that the pH be maintained in theaforementioned 8 to 10 range.

The mixture of reactants is conducted from mixer 11 into reactor 13wherein sulfonation is allowed to proceed to substantial completeness ata pressure which approximates the vapor pressure of water at thereaction temperature. The sulfonated product then passes throughpressure relief valve 14, into flash tank 16. A minor portion of thesulfonated product from the reactor is recycled by pump 15 to the mixer.The recycled sulfonate product is utilized to promote emulsification ofthe reactants in the mixer so that the sulfonation reaction is readilymaintained and'normally comprises about 5% by weight of the total amountof material fed into the system. The amount of sulfonated product whichis recycled can, of course, be varied and is limited in maximum amountonly by economic considerations. It is to be understood that in anyevent a sufficient amount of the sulfonated product is normally recycledso that the emulsification in the mixer is adequate to the maintenanceof the sulfonation reaction.

The flow of reactants to the reactor andthe size of the reactor itselfare normally scaled so that the reactants are in contact in the reactorfor about minutes. As little as 4 minutes reaction time will sufiice inmany cases but sulfonation completeness will be sacrificed to someextent with such short times. The highest possible completeness ofsulfonation can be obtained with a total contact time in the reactor ofabout minutes.

The sulfonation reaction is exothermic in nature. -It is desirable thatthe reaction temperature be maintained in the temperature range fromabout 350 to 400 F., although higher temperatures, up to about 415 F.,can be tolerated for short periods of time. Such high temperaturesshould be avoided, .however, since undesirable side reactions arepromoted and there is atendency for the productto discolor at suchtemperatures. The desired temperature can be conveniently maintained byadjusting the temperature of the reactants emerging from heat exchangers3. and 8 and/or by providing the reactor with suitable temperatureadjusting means.

The term consisting essentially of as used in the definition of theingredients present in the composition claimed is intended to excludethe presence of other materials in such amounts as to interferesubstantially with the properties and characteristics possessed by thecomposition set forth but to permit the presence of other materials insuch amounts as notsubstantially to atfect said propertiesandchal'acteristics adversely.

Having thus described the invention, what is claimed is:

.1. A composition of matter, particularly adapted for use in detergentapplications, consisting essentially of a mixture of sulfonatedaliphatic monoand poly-glyceryl ether compounds of the general 'formulawherein R is an alkyl radical containing from about 8 to 22. carbonatoms, n is an integer from 1 to 4, and X is selected from the groupconsisting of chlorine, hydroxyl and water-soluble sulfonic acid saltradicals, at least one X in each compound of the mixture being asulfonic acidsalt radical, said mixture containing at least about 10% ofsuch sulfonated aliphatic glyceryl ethers where n is 2, the balance ofsaid mixture consisisting predominately of a mixture of such sulfonatedaliphatic glyceryl ethers where n is 1 and 3.

2. The compositions of claim 1 wherein the cation of the water-solublesulfonic acid salt radical is selected from the group Consisting ofsodium, potassium, animonium, calcium, magnesium, andalkylol-substituted ammonium in which the alltylol contains a wholenumber of carbon atoms from 2 to 3.

3. The composition of claim 1 wherein the cation of the water solublesulfonic acid salt radical is sodium.

4. The composition of claim 1 wherein the cation of the water solublesulfonic acid salt radical is potassium.

glyceryl ethers with an aqueous solution of an alkali metal sulfite at atemperature within the range from about 350F. to about 415 F. for fromabout 4 to about 20 minutes, the sulfonation reaction chamber containingfrom about 50% to'about 70% water.

6. A continuous process for preparing a mixture of aliphatic glycerylether sulfonates which comprises separately heating, to a temperaturewithin the range from about 350 F. to about 370 F., an aqueous solutionof an alkali metal sulfite and a mixture of aliphatic glyceryl etherscontaining at least about 10% of aliphatic dichlorodiglyceryl ethers,passing said heated materials through a commingling zone, then passingthe commingled aliphatic glyceryl ether and sulfite solution through areaction zone in from about 4 to about 20 minutes, the temperature ofsaid reaction zone being maintained in the range from about 350 F. toabout 415 F., and recycling a minor portion of the exiting stream beingreleased from the reaction pressure to a lower pressure in a receivingzone. 1

'7. The process of claim 6 wherein the alkali metal sulfite is sodiumsulfite.

8. The process of claim 6 wherein the alkali metal sulfite is potassiumsulfite.

9. The process of claim 7 wherein the water content of the sulfonationreaction mixture is from about 50% to about water.

References Cited in the file of this patent UNITED STATES PATENTS2,010,726 Kirstahler Aug. 6, 2035' 2,094,489 Hueter Sept. 28, 19372,260,753 Marple Oct. 28, 1941 2,706,207 Schnell et al Apr. 12, 1955UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,024,273 March 6 1962 David D. Whyte et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1, line 2 1: for "Strechkerization' read Streckerization column3, line 10, after "alkyl" insert radical column 4 line 15. for "hte"read the column 7, line 7, for "97.7%" read 97.9% column 10 line 19, for"chamber" read mixture Signed and sealed this 10th day of July 1962.

(SEAL) Atteat:

ERNEST w. SWIDER DAVID LADD Atteefin-S Officer Commissioner of Patents

1. A COMPOSITION OF MATTER, PARTICULARLY ADAPTED FOR USE IN DETERGENTAPPLICATIONS, CONSISTING ESSENTIALLY OF A MIXTURE OF SULFONATEDALIPHATIC MONO-AND POLY-GLYCERYL ETHER COMPOUNDS OF THE GENERAL FORMULA2. THE COMPOSITION OF CLAIM 1 WHEREIN THE CATION OF THE WATER-SOLUBLESULFONIC ACID SALT RADICAL IS SELECTED FROM THE GROUP CONSISTING OFSODIUM, POTASSIUM, AMMONIUM, CALCIUM, MAGNESIUM, AND ALKYLOL-SUBSTITUTEDAMMONIUM IN WHICH THE ALKYLOL CONTAINS A WHOLE NUMBER OF CARBON ATOMSFROM 2 TO 3.